Thiophosphoric esters



United States Patent M 3,284,546 THTGPHQSPHURIC ESTERS Raffaello Fusco, Giorgio Rossi, and Pietro de Pietri Tonelli, Milan, and Alberto Barontini, San Donate Milanese, Milan, ltaly, assignors to Montecatini Societa Generale per lllndustria Mineraria e Chimica, a corporation of Italy No Drawing. Filed Oct. 31, 1962, Ser. No. 234,541 Claims priority, application Italy, Nov. 3, 1961, 19,789/ 61 9 Claims. (Cl. 260-4941) This invention is directed to a new class of compounds of the following general formula (1):

PSCIHOOOR2 R O I C R in which R, R and R represent the same or different alkyl radicals of low molecular Weight, having linear or branched chains, saturated or unsaturated, at least one of the R, R R radicals containing one or more fluorine atoms; and R is hydrogen or a phenyl radical, and X stands for oxygen or sulfur. R and R stand preferably for CH C HA F, C H R is preferably a radical selected from the group consisting of CH C H CH CF CHF and C2H4F.

Another object of the present invention is to provide a new process for preparing the compounds of the formula (I). Said process consists in reacting the alkaline 3,284,546 Patented Nov. 8, 1966 R O I C R wherein R, R R R have the above indicated meaning, Me is an alkali metal, and Hal is chlorine or bromine.

The new compounds occur as oily substances which are insoluble in water and soluble in organic solvents. They are characterized by a high activity against parasites, particularly against mites. It is known that it is particularly desirable that substances employed for control of mites display an effective action either against adults or against the eggs, and moreover that they be end-owed with great persistance of activity, namely that they maintain their efficiency for a long time after application.

It has surprisingly been found that the compounds belonging to the class which is the object of the present invention possess said requirements, and some of them to a far greater extent than the products usually employed for control of this type of phytophagous pest.

In this connection, comparison data is reported below, comparing the action of a number of said new compounds toward Metatetranychus ulmi with several products commonly employed as acaricides.

Percent Eggs1ercentages of Active sub mortality of unhatehed eggs Product stance (AS) adults by concentr. direct spraying Direct Residual spraying effect PSCHCOOCH2-CH2F 0.01 27 2 94 H I 0.1 100 100 C2H5O S CeHs 0, 01 4 19 96 /fi-S |CHCO OCH2CH:F 0.1 100 88 100 C1H5O 0 CflH5 PSCHCO OCH:CH:F 0.01 59 3 97 0. 1 100 100 100 CH3 0 S CtHs I Cl-S 0 PG 01 0.01 22 11 22 I 0. 1 33 95. 5 100 C1 Tetraehlordiphenylsulphone (Tedion) O H O. 01 16 0 C1 S0 Cl 0.1 34 29 0 I! 0 P-chlor0phenyl-p-chlorobenzenesulphonate (Ovotran) PS- CH;C ONE-OH 0.01 100 0 None II 0.1 100 87 None (311E150 S OH; (Fae) N OTE: Spraying was carried out on discs 01' apple tree leaves.

Ovicidal effect was determined on eggs laid by untreated females on treated discs, while removing the mites after 24 hours (see Example 21).

No residual effect is noted for the product Fac having highest activity against the adults, although it possesses also a remarkable ovicidal action upon direct spraying. Tedion acts efiiciently as ovicide by direct spraying and shows moreover a residual effect. However, it displays, to a lesser extent, activity against adults. Ovotran is slightly superior to the preceding compound in respect to activity against adults. However, it is inferior in regard to ovicidal action, and residual effect. The three new compounds, included in the class which is object of the present invention, show a more complete action spectrum against mites, since they possess the considered three characteristics to a high degree.

Persistance of activity, either against eggs or adult mites, of the new compounds was confirmed also by field tests described in Examples 22 and 23.

Furthermore, it has been found that the compounds comprised in the claimed class act according to a special mechanism which inhibits the hatching of the eggs, which the females lay after having been in contact with the active compounds or after ingesting them (or their metabolites), on untreated leaves (see Example 31 Table XIII and Example 32Table XIV).

It has also been found that the compounds comprised in the general formula (1) are active against hibernant eggs.

This is an important practical characteristic, since hibernant eggs (laid between the end of summer and late autumn and hatching in spring) are notoriously much more resistant towards the action of the pesticides than the summer eggs of the mites (see Example 33--Table XV).

Finally, they have also an outstanding action against the insects as hereunder demonstrated:

Four days old newborn of Locusta migratoria migratoricides (Orthoptera) fed with leaves of graminacea treated by spraying with solutions containing 1/.,., (1 part per thousand) of active substances are totally destroyed within 48 hours after treatment with the products obtained in Examples 5, 7, 8, and 80% destroyed with that of Example 6.

The aphid Acyrthosiphon onobrychl's (Emiphtera) is wholly destroyed, within 24 hours from treatment, by spraying with solutions containing l of active substances on broad bean seedlings, previously infested, said substances being those of Examples 5, 6, 7, 8. Teclion (2,4,5,4 tetrachlorodiphenylsulfone) kills, under the same conditions, 69% thereof.

On newborn larvae (2 days old) of Pier-is brassicae (Lepidoptera), transferred to cabbage leaves gathered one day after treatment of the plants with solutions containing 1/ of active substances, the following results were obtained, after 24 and 72 hours of stay of larvae on the leaves.

N-methyl-l-naphthylcarbamate, usually employed against larvae of Lepidoptera.

Newborn larvae of Carpocapsa pomonella (Lepidoptera) transferred, 24 hours after treatment, to small apples which have been treated with solutions containing 1% of active substances, were killed to the extent of 100% with the product obtained in Example 5, 33% with that of Example 6, 57% with that of Example 7, and 100% with that of Example 8.

Adult specimens of Musca domestica (Diptera), after a stay of 24 hours in Petri dishes of 85 mm. diameter treated with 100 active substance for each dish, were totally destroyed with the products obtained in Examples 5, 6, 7, 8.

Four days old larvae of Aedes aegypti (Diptera,

mosquito) which were left for 24 hours in a water solu-- tion containing one part per million of active substance, were 100% destroyed by the product obtained in Example 5, 33% by that of Example 6, 4% by that of Example 7, and 100% by that of Example 8.

Newborn larvae (2-3 days old) of Chrysomela decemlirzeata (Coleoptera) sprayed with solutions containing 196 of active substances were 100% destroyed by the products of Examples 5, 7, 8, and 30% with that of Example 6.

From what it is stated hereinabove, and from the supporting data presented below, it is clearly evident that the compounds comprised in the general formula of the present invention have a particularly wide spectrum of action, and they must thus be considered agents having outstanding efiiciency against pests.

The compounds in accordance with the present invention may be formulated without difficulty by conventional means. The compounds of the invention may be used either as sole active ingredient or in admixture with each other or in admixture with other pesticides having a different activity.

A preferred way is to formulate the compositions as emulsifiable liquids, which are obtained by dissolving the active substances or substances in suitable solvents or mixture of solvents, together with one or more surface active substances added to make the preparation emulsifiable in water.

For special purposes, the substances of the present invention may be formulated as powders for dry dusting, by direct admixture of the active substance or substances with inert substances such as talc, pyrophyllite or china clay, or as wettable powders by direct admixture of the active substance with inert substances such as kieselguhr, clay, attapulgyte, and surfactants, which make the formulated compound dispersible in water.

Toxicity data toward cold-blooded animals is presented below. The indicated values represent the L.D. (lethal dose) 50 expressed in mg./kg. of treated animal (white mouse).

At these doses no mortality occurs.

The following examples are reported to illustrate the process of preparation, and also the acaricide and ovicide activity of the compounds belonging to the claimed class, as well as the formulations containing them. It is to be understood that said examples are not intended to restrict the scope of the present invention.

EXAMPLE 1 80 ml. of acetone solution of potassium salt of BB-difluoro-ethyl-dithiophosphoric acid of titer 2.5 mol/ lit. are added to 21.6 g. (0.2 mole) methyl chloroacetate; the solvent is kept at reflux for 1 hour. The reaction mixture is cooled and diluted with 200 ml. water; the organic phase is decanted, taken up again with 50 ml. methylene chloride and washed with water. After solvent removal under reduced pressure, 34.5 g. of oily substance are obtained as residue, said substance constituting the methylester of [3/3-difluorethyl-dithio-phosphorylacetic acid, i.e.

The product purified by distillation under reduced pressure has a boiling point of 0.8 mm. Hg=154156 C., and its P found=10.45.40%; P ca1c.=10.49%.

EXAMPLE 2 64 ml. of acetone solution of potassium salt of fiB-difiuorethyl-dithiophosphoric acid of titer 2.5 mol/lit. are added to 19.6 g. ethyl chloroacetate; the solvent is then kept at reflux for 30 minutes. The reaction mixture is then cooled at room temperature and filtered by suction from the formed KCl. The acetone solution is diluted with water; the separated oily phase is taken again with 40 ml. of methylene chloride and washed with water. After solvent evaporation under reduced pressure, 29 g. of an oily substance are obtained comprising the ethylester of ,Bfl-difluorethyl-dithio-phosphoryl acetic acid of the formula:

/:fi-S-CHzCOO-C2H5 F-CHz-CH2O S Said substance can be purified by distillation. Its boiling point at 0.2 mm. Hg is 149 151 C. Its phosphorous con-tent is: P found=9.759.73%; P calc.=10.05%.

EXAMPLE 3 A water solution containing 0.12 mole of potassium salt of Bfi-fluorethyl dithiophosphoric acid is added to 31.2 g. bromophenyl acetate of 3-methyl-butin-1-ol-3 (boiling point at 0.4 mm. Hg=113-116 C.) diluted with 25 ml. acetone; the mixture is kept at 5060 C. for 30 minutes. After evaporating most of the solvent under reduced pressure, the reaction mixture is extracted with 30 ml. methylene chloride. 32 g. of oily substance are left as residue from the chloromethylene extract obtained after washing with water and evaporating under reduced pressure. Said substance is prevailingly constituted of 3-methylbutylester of BB-difluoroethyl-dithiophosphoryl-phenyl-acetic acid of the formula:

which shows P found=6.20-6.16%; P calc.=7.33%.

EXAMPLE 4 118 ml. of a water solution of sodium salt of flp-difluorethyl-dithiophosphoric acid of titer 1.98 mol/ lit. are added to 48.6 g. a-bromophenylacetate diluted with 70 ml. acetone; the mixture is stirred at room temperature (about 20 C.) for 50 hours. The reaction mixture separates in an organic phase which is concentrated to a small volume under reduced pressure, and in an aqueous phase which is extracted with 25 ml. methylene chloride. The evaporation residue is combined with chloromethylene extract, then washed with water, dried upon CaCl and reduced to dryness under reduced pressure. A 74 g. residue is obtained in the form of faint yellow oil, consist- 6 ing of ethyl ester of 5,8-difluorethyl-dithiophosphoryl-phem yl-acetic acid of the formula:

F-CHr-CHgO Ps CHCO0-C2H5 F-CHz-CHrO S 06 which upon analysis shows: P found=7.727.73%; P calc.=8.09%.

This product after a time solidified totally to a compact mass (M.P.=4143 C., from ligroin).

EXAMPLE 5 71.4 ml. of a water solution of sodium salt of diethylphosphoric acid (titer 3.22 mol/lit.) are added to 52.5 g. a-bromophenyl-acetate of ,B-fiuorethyl alcohol diluted with 70 ml. acetone; the mixture is stirred. Owing to the exothermic reaction, the temperature rises from 20 to 30 C. After stirring for 15 hours, the mixture separates in an organic phase which is concentrated to a small volume under reduced pressure, producing an aqueous phase which is extracted with 25 ml. methylene chloride.

The evaporation residue is combined with chloromethylene extract, then washed with dilute sodium bicarbonate solution, then with water, and afterwards dried upon CaCl and reduced to dryness under reduced pressure. 69 g. of a reddish oil are left consisting of the [i-fluoroethylester of diethyldithiophosphoryl-phenyl acetic acid of the formula:

PsoHooooHroH2F C2H5O S 06115 which on analysis shows: P found=8.088.ll%; P calc.=8.45%.

EXAMPLE 6 118 ml. of an aqueous solution of the sodium salt of Bfl-difluoroethyl-dithiophosphoric acid (titer 1.98 mol/ lit.) are added to 52.2 to bromophenylacetate of fi-fiuorethyl alcohol diluted with 70 ml. acetone. The mixture is stirred at room temperature (2023 C.) for 15 hours. The organic layer which separates is poured into 50 ml. water, taken up again with 30 ml. methylene chloride, washed once more with water, then dried on CaCl and evaporated under reduced pressure. 72.7 g. -of an orangeyellow oil are left, constituted of the B-fiuorethylester of flB-difluorethyl-dithiophosphoryl phenylacetic acid of the formula:

PsrlJHooooH7-oHlF FCH2CH20 CaHs which on analysis shows P found=7.04-7.09%; P calc. =7.69%.

EXAMPLE 7 41.6 g. potassium diethyl mono-thiophosphate and 52.2 g. bromophenyla-cetate of fl-fluorethyl alcohol are mixed with 70 ml. acetone.

The reaction is exothermic. The reaction mixture is kept to solvent refluxing for 1 hour, then is stirred at room temperature for further 24 hours. The formed KBr is filtered olf by suction, then most of the solvent is removed under reduced pressure. The residue is poured into 50 ml. water, taken up again with methylene chloride, washed 'with water, then with a NaHCO dilute solution and finally once more with water.

After drying upon CaO1 and evaporation under reduced pressure, 64.5 -g. of an orange-yellow oil are obtained, consisting of the fl-firuorethylester of diethyl monothiotphosphoryl-phenylacetic acid of the formula:

having the following analysis P found=8.21%; P callc. =8.84%.

7 EXAMPLE 8 92.7 ml. of a water solution of the sodium salt of dimethyl-dithiophosphoric acid (liter 2.48 mol/lit.) are added to 52.8 g. bromophenyl-acetate of B-fluorethyl alcohol, diluted with 80 ml. acetone; then the mixture is stirred at room temperature (20-23 C.) for 20 hours. The organic phase is separated :by decantation, and is reduced to a small volume under reduced pressure and poured into 50 ml. water. After being taken up again with 30 ml. methylene chloride, washed with water, dried on CaCl and evaporated under reduced pressure, 59.7 g. of a light reddish oil are obtained, consisting of the B-fiuorethylester of dimethyl-dithiophosphoryl phenylacetic acid of the formula:

PSCHCOO-CH2OHZF CHgo Ja which on analysis shows: P -found=8.83-8.85%, P calc. =9.15%.

EXAMPLE 9 49 ml. of a water solution of sodium salt of diethyl dithiophosphoric acid (titer 3.22 mol/ lit.) are added to 21 g. ohloroacetate of p-fluorethyl alcohol diluted with 50 ml. acetone; the mixture is stirred at about 25 C. for 10 hours. The reaction mixture is diluted with 70 ml. water, and the organic layer is separated by decantation and reduced to small volume under reduced pressure. The residue is taken up again with 30 ml. methylene chloride, washed with water, dried on CaCl and evaporated under reduced pressure. 38.5 g. of a light yellow oil are obtained as residue, consisting of the fi-fiuorethylester of diethyl dithiophosphorylacetic acid of the formula:

showing, on analysis, P found=10.79l0.85%; P calc.

EXAMPLE 10 69 m1. of a water solution of the sodium salt of B 8difluorethyl-dithiophosphoric acid (titer 1.84 mol/lit.) are added to 15.5 g. chloroacetate of B-fiuorethyl alcohol diluted with 40 ml. acetone; the mixture is then stirred at room temperature for 30 hours. The organic phase is separated, evaporated under reduced pressure, and the residue poured into 35 ml. water. It is then separated, taken up again with methylene chloride and washed once more with water. After drying on CaCl and evaporating under pressure, 28 g. of [light yellow oil are obtained, consisting of the fl-fiuorethylester of BB-difluorethyl dithiophosphorylacetic acid, having the formula:

F--OH3CH2O PSCHz-COO--CH2-CH2F FCH2CH2O S which, on analysis, shows: P found=9.159.20%; P calc.=9.49%.

EXAMPLE 11 65.6 g. bromophenylacetate of 2,2-3,3-tetrafluoropropyl alcohols diluted with 30 ml. acetone are added to 44.8 g. potassium diethyl dithiophosphate in 50 ml. acetone. The reaction is exothermic. The reaction mixture is stirred at 20-25 C. for'6 hours, the refluxing of the solvent being continued for half an hour. After cooling at room temperature, the mixture is poured into 100 ml. water; the organic phase is separated and most of the acetone is evaporated under reduced pressure. The residue is taken up again with 50 ml. methylene chloride, then washed with water, then with diluted NaHCO solution, and finally once more with water. After drying on CaCl and evaporation under reduced pressure, 76.8 g. oil are obtained, consisting of the 2,2-3,3-tetrafluoropropylester calc.=7.l3

EXAMPLE 12 94 ml. of a Water solution of the sodium salt of Bfl-difluorethyl dithiophosphoric acid (titer 1.84 mol/lit.) are added to 49.2 g. bromophenylacetate of 2,2-3,3-tetrafluoropropyl alcohol diluted with 50 ml. acetone; the mixture is stirred at a temperature in the range 20-25 C. for 9 hours. The organic phase is separated and concentrated under reduced pressure; the residue is taken up again with 30 m1. methylene chloride and washed with water, then with diluted NaCHO solution and finally once more with water. After drying on CaCl and evaporation under reduced pressure, a residue is obtained of 61.5 g. oily product, consisting of the 2,2-3,3-tetrafluoropropylester of pfl-difluoroethyl dithiophosphoryl phenylacetic acid of the formula:

FCH2CH2O /l|SCH-COOCHzOFz-CHF2 FCH OHzO SI 05H: which, on analysis, shows: P found=6.43-6.44%, P calc.=6.58%.

EXAMPLE 13 23.8 g. bromophenyl acetate of 2,2-3,3-tetrafluoropropyl alcohol diluted with 15 ml. acetone are added to 15.6 g. sodium dimethyl-dithiophosphate dihydrate in 25 ml. acetone. A mild exothermic reaction occurs. The mixture is stirred at about 25 C. for 10 hours, and is then diluted with 30 ml. water, and the organic phase separated. The latter is concentrated under reduced pressure, and the residue is then taken up again with 20 ml. methylene chloride. After washing with water, and then with NaHCO diluted solution, and finally once more with water, the residue is dried on CaCl and evaporated under reduced pressure, obtaining as residue 23.5 g. oily substance, consisting of the 2,2-3,3-tetrafiuoropropylester of dimethyl dithiophosphoryl phenylacetic acid of the formula:

CH O

/f-SCH-OOOCHr-CF2CHF2 CH3O S (IJBHG showing, on analysis, P found=7.497.50%; 'P calc.= 7.62%.

EXAMPLE 14 27 g. of potassium [3p-difluoroethyl-thiophosphate and 24.3 g. of a-ethyl bromophenylacetate are mixed in cc. of acetone while agitating. The mixture is heated to 40 C. for 2 hours and is kept at room temperature for 20 hours. Most of the solvent is eliminated under reduced pressure and the residue is poured into 60 cc. of H 0. The oil thus obtained is extracted with 50 cc. of methylene chloride and is dried on CaCl After complete elimination of the solvent under reduced pressure 29.5 g. of an oily liquid essentially consisting of the ethylene ester of flB-difluoroethyl thiophosphorylphenyl acetic acid, are obtained.

FCHzCHzO Analysis.P calc.=8.4l%. P found=8.038.09%.

F CHzCHzO P--SCH2-C O 011201121 Analysis.-P calc.-=9.98%. P found=9.619.60%.

EXAMPLE 16 27 g. of potassium fiB-difluoroethyl-thiophosphate and 26 g. of fl-fluoroethyl a-bromophenylacetate are mixed with 100 cc. of acetone while agitating.

By operating as indicated in Example 1, 26 g. of an oily liquid are obtained. This liquid is then purified by dissolving it in 50 cc. of CH Cl and then precipitating with 110 cc. of petroleum ether.

The oily fraction thus precipitated is collected and solvent traces are eliminated.

8 g. of an oily liquid prevailingly consisting of the 8- fiuoroethylester of BB-difluoroethyl-thiophosphorylphenyl acetic acid are obtained.

Analysis.P calc.':8.02%. P found=7.447.66%.

EXAMPLE 17 A spraying formulation, which may be profitably employed in the control of acarids and the eggs thereof, may be prepared by dissolving 20 parts of the B-fluoroethylester of diethyl dithiophosphoryl phenylacetic acid in 77 parts xylene, and by adding 2 parts of an anionic surfactant selected from the class of alkylarylsulphonates or alkylsulphates, and 1 part of a non-ionic surfactant selected from the class of ethylene oxide condensation products with fatty acids or with fatty alcohols or alkylphenols.

EXAMPLE 18 A spraying formulation, which may be employed against acarids and the eggs thereof, is prepared by dissolving 20 parts of fi-fluoro-ethylester of Bfl-difiuoroethyl dithiophosphorylacetic acid in 75 parts xylene and adding 2.5 parts of an anionic surfactant selected from the class of alkylarylsulphonates or alkylsulphates and 2.5 parts of a non-ionic surfactant selected from the class of ethylene oxide condensation products with fatty acids, or alcohols, or with alkyl-phenols.

EXAMPLE 19 A spraying formulation, which may be employed in the control of acarids and their eggs is prepared by dissolving parts of B-fluoro-ethylester of dimethyldithiophosphoryl phenylacetic acid and 20 parts of a-cyanisoproylamide of O,O-diethyl diphosphoryl acetic acid in 67 parts xylene, while adding 2 parts of an anionic surfactant selected from the class consisting of al-kylarylsulphonates or alkylsulphates, and 1 part of a non-ionic surfactant selected from the class consisting of the ethylene oxide condensation products with fatty acids or alcohols or with alkylphenols.

10 EXAMPLE 20 A wcttable powder may be suitably prepared by mixing 3-5% of a compound belonging to the claimed class together with 97-95% talc.

EXAMPLE 21 A wettable powder may be suitably prepared by mixing 20% of a compound belonging to the claimed class together with 75% diatomaceous earth and 5% of an anionic surfactant, selected from the class consisting of alkylarylsulphonates or alkylsulphates.

In the following example, are reported data relating to the activity, against mite adults and mite eggs, of a number of the prepared compounds. The determinations where carried out according to the hereinafter indicated procedure on the following test mites:

(1) Metatetranychus ulmi, susceptible strain (S) and strain (R) resistant to the action of other acaricides;

(2) Tetranychus telarius.

All the tests on Tetranychus telarius were carried out on bean plants in pot. With Metatetranychus ulmi, strain (S) and (R), the tests were partially performed on pot bred apple trees, partially on field bred apply plants. The following technique was employed for carrying out the tests:

(1) Tests on pot plants.--Discs having a diameter of 2.8 cm. are recovered from apple or bean leaves and sprayed with the products under tests before or after having been infested with the adults.

(2) Tests on field plants.Apple plants are sprayed with the products at 0.02% of active substance, before or after infecting them with mites; some leaves are then sampled at successive time intervals, while obtaining therefrom discs of 2.8 cm. diameter.

EXAMPLE 22 Activity against adults is determined by direct spraying at Metatetranychus ulmi S, on discs of apple tree leaves, in the laboratory.

Discs are infested, on the upper leaf face, each with 60 adult females, then sprayed with the products to be tested and kept for 48 hours in open Petri dishes as 24-26 C.

Percentage motalities, determined with a stereomicroscope, are reported in Table I.

Ovicide activity is determined by direct spraying eggs of Metatetranychus ulmi S on discs of apple tree leaves, in the laboratory.

Discs are infested, each with 100 adult females; after 24 hours the females are removed, and the discs together with eggs are sprayed with the products to be tested and kept, at 2426 C., in open Petri dishes for a few days beyond the hatching date of unsprayed eggs (check).

The ascertained percentages of unhatched eggs are reported in Table II.

Table II Product obtained in Active substance con- Unhatched eggs,

Example centration, percent EXAMPLE 24 Residual effect against eggs of Metatetranychus ulmi S, for a short time (at most about 26 hours) after treat- 12 EXAMPLE 2s Persistance of activity is determined against eggs of Metatetranychus-ulmi S, laid by untreated females on apple tree leaves treated on the field (date of treatment of plants: May 9, 1961).

Plants are sprayed with the products at 0.02% of active substance, then 1, 3, 6, 13 and 18 days after the day of treatment 8 leaves are gathered from each plant. From the leaves are obtained the discs, which are infested partly on the upper side and partly on the underlying side of the leaf, each with 100 adult females. After 24 hours the mites are removed, and the discs together with eggs are kept inside of open Petri dishes, for a few days beyond the hatching date of untreated eggs. The results are reported in Table IV.

ment.

The eggs are laid by untreated females on discs of apple T bl IV tree leaves in the laboratory. a 8

Discs are sprayed with the products to be tested and after two and half hours are infested, each with 100 adult 25 Percentage unhatched egg-s females; after 24 hours the females are removed and the ogzgodugt dsldesiziggg In discs together with the eggs are sprayedav th the product ggfi Z? 1 3 6 13 18 to be tested and kept, at 242 6 C., inside open Petri day days days days days dishes, for several days beyond the hatching date of unsprayed eggs. The ascertained percentages of unhatched 5 100 100 99 96 72 100 100 98 50 49 eggs are reported in Table III. 6 99 9 96 93 95 99 100 98 52 73 Table III 7 97 97 95 69 73 100 100 100 4 14 8 100 100 9s 84 51 Product obtained Active substance Con- Unhatched eggs, 100 99 9 0 0 in Example centration, percent I=1eaf underside; U=leat upper side. 1 0. 01 1 0.1 99 1 100 4 .21 g

1' 100 EXAMPLE 26 6 o. 01 77 33 Persistance of activity against eggs of Metatetranychus 7 8- 2 3% ulmi S, laid by untreated females upon apple tree leaves 1' 100 treated on the fields (date of plant treatment: June 14, 8 8 33 1961). The test is carried out according to the process 1 100 described in Example 22. The results are reported in Table V.

Table V Percentage of unhatched eggs Products obtained in- 1 3 6 12 18 24 30 day days days days days days days Example 5:

I 1 100 100 87 1o 3 3 U 100 100 97 64 4 1 Example 6:

I. 88 95 92 92 73 74 U 98 93 97 94 89 77 72 Example 7:

I. 96 95 96 31 9 7 U 99 97 55 33 14 8 Example 8:

I. 99 89 22 1 1 U 100 100 56 16 5 o Tetrachlorodiphenylsulphone l I=1eaf underside; U=1eat upper side.

13 EXAMPLE 27 Persistance of activity against adults of Metatetranychus ulmi S, on apple tree plants on the field.

Persistance of activity against adults is determined by measuring percentage mortality, at diiferent time intervals after treatment (1, 3, 6 and 13 days), of the adults removed after 24 hours of contact with the surface of treated leaves, according to Example 22.

The results are reported in Table VI.

Table VI Product Side egg Percentage of mortality obtained in deposition Example on leaf surface 1 day 3 days 6 days 13 days *I=u.uder side leaf; U=upper side leaf.

EXAMPLE 28 Activity against adults and eggs of Metatetranychus Table VI I Eggs Adults Number of adults observed Product obtained Percent on 100 leaves in Example Number of unof eggs hatched observed eggs Before 2 days 13 days treatment after after treatment treatment EXAMPLE 29 Activity against adults is determined by residual effect a short time (24 hours) after treatment, on Metaletranychus ulmi susceptible strain S and resistant strain R.

The test was carried out in the field by spraying (on July 25, 1961) young apple trees with the products under examination at a concentration 0.02% of active substance. 24 hours after treatment 5 leaves per plant are gathered; from said leaves the discs are obtained whereupon adult mites belonging to the two above-mentioned strains are allowed to rest for 24 hours. The results are reported in Table VIII.

I=under side leaf; U=upper side leaf.

ulmz' S is determined by direct spraying on apple tree plants, on the field. The plants are infested with mites in the field and after about one month are sprayed with the products under examination, at 0.02% concentration of active substance.

24 hours after treatment 5 leaves per plant are gathered; the discs obtained from the leaves are kept at 2426 C. inside open Petri dishes for several days beyond the hatching date of unsprayed eggs; then the percentages of unhatched eggs are determined, which are reported in Table VII.

In the same table the activity values against adults are reported, obtained by determining the number of females present on the leaves before the spraying and at different time intervals after the spraying.

EXAMPLE 3O Persistence of activity is determined against eggs of Metatetranychus ulmi susceptible strain S and resistant strain R, said eggs being laid by untreated females on leaves of apple trees sprayed on the field.

Plants are sprayed with the products at a concentration 0.02% of active substance, and then, 1, 3, 6, 14 and 20 days after the treatment date, 8 leaves are gathered from each plant. From the leaves discs are obtained which are infested with about adult females. After 24 hours, the acarids are removed and the discs together with the eggs are kept at 2426 C. inside of open Petri dishes for a number of days beyond the hatching date of untreated testimony eggs. The results are reported in Table Table IX Percentage of unhatched eggs 7 Side of egg deposition Product obtained in Example on leaf 1 day 3 days 6 days 14 days 20 days surface 1 S R S R S R S R S R Cl C 02- 01 U. 70 38 6 8 0 Tetrachlorodiphenylsulphone 1 I=under side leaf; U=upperside leaf. S=susceptible strain; R=resistant strain.

EXAMPLE 31 EXAMPLE 33 Activity against adults of Tetranychus telarius, on discs of bean leaves, in the laboratory.

Discs are infested, each with 60 adult females, then sprayed with the products under examination and kept for 48 hours inside of open Petri dishes, at 2436 C.

The mortality percentages are reported in Table X.

Table X Product obtained in Active substance con- Mortality, percent Example centration, "/00 EXAMPLE 32 Activity against eggs of Tetranychus telarius by direct spraying, on discs of bean leaves, in the laboratory.

Discs are infested, each with 50 adult females; after 24 hours the females are removed and the discs are sprayed with the products under examination and kept at 2426 C. inside of open Petri dishes for several days beyond'the hatching date of the untreated testimony eggs. The noted percentages of unhatched eggs are reported in Table XI.

Table XI Product obtained in Example Active substance con- Mortality, percent centration, "/00 Residual effect towards eggs of Tetranychus telarius a short time (at most about 26 hours) from treatment. The eggs are laid by untreated females on discs of bean leaves, in the laboratory.

The discs are sprayed with the product under examination, and after two and a half hours they are infested each with adult females. After 24 hours the mites are removed, and the discs are kept at 24-26 C. inside of open Petri dishes for several days beyond the hatching date of unsprayed eggs. The noted percentages are reported in Table XII.

Ovicidal activity displayed by the active substances when sprayed on females of Metatetranychus ulmi on discs of apple tree leaves.

Discs obtained from apple tree leaves, infested with females of Metatetranychus ulmi, are treated with the substances under test. After two hours the females are transferred to discs of untreated leaves and kept on wetted cotton in Petri dishes. The females are allowed to lay eggs for 24 hours, when they are eliminated. The percentage of unhatched eggs is then calculated. The results obtained are reported in Table XIII.

Table XIII Percentage of unhatched eggs Product obtained in Example 1 7 EXAMPLE 3s Ovicidal activity is determined by the effect of the active substances on females feeding upon the product absorbed by leaves. The substances under test, diloted in water, are distributed dropwise, by means of a microsyringe, on the upper face of leaves of bean and apple plants bred in pots. After a pre-established time interval the females of T. telarius and M. ulm i are transferred onto the underlying, untreated face of the same leaves and the mites are kept confine-d thereon by means of lanolin. They are allowed to feed and lay eggs for 24 hours, and the females are then eliminated. The percentage of unhatched eggs, laid on the underlying, un treated, face of the leaves is calculated. The results are reported in Table XIV.

Table XIV Percentage of unhatch- Product obtained ed eggs laid on the Effect of the hereinafter mentioned products on hibernant eggs of Metatetranychus ulmi.

Date of the treatment: March 26, 1962.

Beginning of the hatching of the eggs: about April 15.

The term lower alkyl means alkyl radicals having up to six carbon atoms.

We claim: 1. A phosphoric acid ester of the formula:

\PS-OH-O 0 OR; RrO i i R in which R, R and R are taken from the group consisting of lower alkyl, lower alkenyl, lower alkyny l, fluorolower alkyl, fluoro-lower alkenyl, and fluorolower alkynyl; at least one of the R, R and R radicals being one of said fluoro radicals; R being taken from the class consisting of hydrogen and phenyl; X being taken from the class consisting of sulfur and oxygen. 2. A phosphoric acid ester of the formula:

PSCH-COOR2 R10 X C0115 wherein R, R and R are taken from the radicals consisting of lower alkyl, lower alkenyl, lower alkynyl, fluorolower alkyl, fluoro-lower alkenyl and fluoro-lower alkynyl; at least one of R, R and R being one of fluoro radicals, and X is taken from the group consisting of sulfur and oxygen.

3. Methyl ester of fiB-difluoroethyl dithiophosphorylacetic acid.

4. ,8 Fluoroethylester of diethyl dithiophosphoryl phenylacetic acid.

5. fl-Fluoroethylester of ppadifluoroethyl dithiophosphoryl phenylacetic acid.

6. ,B-Fluoroethylester of diethyl mono-thioiphosphoryl phenylacetic acid.

7. fi-Fl uoroethylester of dimethyl dithiophosp'horyl phenylacetic acid.

8. fl Fluoroethylester of fiB-difluoroethyl dithiophosphorylacetic acid.

9. Ethylester of [3B diflu'oroethyldithiophosphoryl The results are reported 1n Table XV. 4O phenylacetic acid.

Table XV Product Active suhst. Total number Number of Percent unobtained in concentrationlos of eggs unhatched eggs hatched eggs Example References Cited by the Examiner UNITED STATES PATENTS 2,927,882 3/1960 Trademan et al. 16722 2,939,876 6/1960 Cramer et al 260461 2,945,780 7/1960 Jones et al. 167--22 2,947,662 8/ 1960 Fusco et a1 260461 XR 3,032,579 5/1962 Losco et a1 260--461 XR 3,047,459 7/1962 Perini et al. 260461 XR 3,076,009 1/19-63 Schrader et al. 260461 3,081,332 3/1963 Ailman et a1 260461 OTHER REFERENCES Kabachnik et al., Chem. Abst., col. 54, vol. 8594 CHARLES B. PARKER, Primary Examiner.

IRVING MARCUS, Examiner.

F. M. SIKORA, Assistant Examiner. 

1. A PHOSPHORIC ACID ESTER OF THE FORMULA: R1-O-P(=X)(-O-R)-S-CH(-R3)-COO-R2 IN WHICH R, R1 AND R2 ARE TAKEN FROM THE GROUP CONSISTING OF LOWER ALKYL, LOWER ALKENYL, LOWER ALKYNYL, FLUORO- LOWER ALKYL, FLUORO-LOWER ALKENYL, AND FLUOROLOWER ALKYNYL; AT LEAST ONE OF THE R, R1, AND R2 RADICALS BEING ONE OF SAID FLUORO RADICALS; R3 BEING TAKEN FROM THE CLASS CONSISTING OF HYDROGEN AND PHENYL; X BEING TAKEN FROM THE CLASS CONSISTING OF SULFUR AND OXYGEN. 